Supramolecular Strategy Effects on Chitosan Bead Stability in Acidic Media: A Comparative Study

Chitosan beads attract interest in diverse applications, including drug delivery, biocatalysis and water treatment. They can be formed through several supramolecular pathways, ranging from phase inversion in alkaline solutions, to the ionic crosslinking of chitosan with multivalent anions, to polyelectrolyte or surfactant/polyelectrolyte complexation. Many chitosan bead uses require control over their stability to dissolution. To help elucidate how this stability depends on the choice of supramolecular gelation chemistry, we present a comparative study of chitosan bead stability in acidic aqueous media using three common classes of supramolecular chitosan beads: (1) alkaline solution-derived beads, prepared through simple precipitation in NaOH solution; (2) ionically-crosslinked beads, prepared using tripolyphosphate (TPP); and (3) surfactant-crosslinked beads prepared via surfactant/polyelectrolyte complexation using sodium salts of dodecyl sulfate (SDS), caprate (NaC₁₀) and laurate (NaC₁₂). Highly variable bead stabilities with dissimilar sensitivities to pH were achieved using these methods. At low pH levels (e.g., pH 1.2), chitosan/SDS beads were the most stable, requiring roughly 2 days to dissolve. In weakly acidic media (at pH 3.0⁻5.0), however, chitosan/TPP beads exhibited the highest stability, remaining intact throughout the entire experiment. Beads prepared using only NaOH solution (i.e., without ionic crosslinking or surfactant complexation) were the least stable, except at pH 5.0, where the NaC₁₀ and NaC₁₂-derived beads dissolved slightly faster. Collectively, these findings provide further guidelines for tailoring supramolecular chitosan bead stability in acidic media.